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EP1383857B1 - Use of metal complex compounds as oxidation catalysts - Google Patents

Use of metal complex compounds as oxidation catalysts Download PDF

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Publication number
EP1383857B1
EP1383857B1 EP02740514A EP02740514A EP1383857B1 EP 1383857 B1 EP1383857 B1 EP 1383857B1 EP 02740514 A EP02740514 A EP 02740514A EP 02740514 A EP02740514 A EP 02740514A EP 1383857 B1 EP1383857 B1 EP 1383857B1
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EP
European Patent Office
Prior art keywords
substituted
unsubstituted
alkyl
hydrogen
metal complex
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP02740514A
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German (de)
English (en)
French (fr)
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EP1383857A2 (en
Inventor
Gunther Schlingloff
Torsten Wieprecht
Frank Bachmann
Joseph Dannacher
Marie-Josée DUBS
Menno Hazenkamp
Grit HÄNSLER
Brigitte Schmidt
Albert Schneider
Peter Weingartner
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BASF Schweiz AG
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Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
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Priority to EP02740514A priority Critical patent/EP1383857B1/en
Publication of EP1383857A2 publication Critical patent/EP1383857A2/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/68—One oxygen atom attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
    • C07F13/005—Compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/15—Locally discharging the dyes
    • D06P5/153—Locally discharging the dyes with oxidants
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1036—Use of compounds accelerating or improving the efficiency of the processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B01J2231/72—Epoxidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/842—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/16—Bleaching ; Apparatus therefor with per compounds
    • D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides

Definitions

  • the present invention relates to the use of metal complex compounds with terpyridine ligands as oxidation catalysts.
  • the present invention relates also to formulations comprising such metal complex compounds, to novel metal complex compounds and to novel ligands.
  • the metal complex compounds are used especially for improving the action of peroxides, for example in the treatment of textile material, without at the same time causing any appreciable damage to fibres and dyeings.
  • FR-2677766 discloses a sensor for measuring the quantity of a component in solution.
  • FR-2677766 teaches the use of Co(II)- complexes of (2,2',6',2"-terpyridine) and (4'-tolyl-2,2',6',2"-terpyridine) as mediators for an oxidation reaction.
  • US 4690895 discloses 2,2',6',2"-terpyridine derivatives, which are complexed by Fe, Co, Ni and Cu. These compounds are useful as dyes having high wet heat-fastness.
  • Peroxide-containing bleaching agents have been used in washing and cleaning processes for some time. They have an excellent action at a liquor temperature of 90°C and above, but their performance noticeably decreases with lower temperatures. It is known that various transition metal ions, added in the form of suitable salts, or coordination compounds containing such cations catalyse the decomposition of H 2 O 2 . In that way it is possible to increase the bleaching action of H 2 O 2 , or of precursors that release H 2 O 2 , or of other peroxo compounds, the bleaching action of which is unsatisfactory at lower temperatures.
  • the aim of the present invention was, therefore, to provide improved metal complex catalysts for oxidation processes which fulfil the above demands and, especially, improve the action of peroxy compounds in an extremely wide range of fields of use without giving rise to any appreciable damage.
  • the mentioned C 1 -C 18 alkyl radicals are generally, for example, straight-chain or branched alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or straight-chain or branched pentyl, hexyl, heptyl or octyl.
  • the mentioned alkyl radicals can be unsubstituted or substituted e.g.
  • aryl radicals that generally come into consideration are phenyl or naphthyl unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, cyano, nitro, carboxyl, sulfo, hydroxyl, amino, N-mono- or N,N-di-C 1 -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, N-phenylamino, N-naphthylamino, phenyl, phenoxy or by naphthoxy.
  • Preferred substituents are C 1 -C 4 alkyl, C 1 -C 4 alkoxy, phenyl and hydroxy. Special preference is given to the corresponding phenyl radicals.
  • Halogen is generally especially chlorine, bromine or fluorine, special preference being given to chlorine.
  • alkali metal cations such as lithium, potassium and especially sodium
  • alkaline earth metal cations such as magnesium and calcium
  • ammonium cations are preferred.
  • Suitable metal ions for Me are e.g. manganese in oxidation states II-V, titanium in oxidation states III and IV, iron in oxidation states I to IV, cobalt in oxidation states I to III, nickel in oxidation states I to III and copper in oxidation states I to III, with special preference being given to manganese, especially manganese in oxidation states II to IV, preferably in oxidation state II.
  • manganese in oxidation states II-V titanium in oxidation states III and IV
  • iron in oxidation states I to IV cobalt in oxidation states I to III
  • titanium IV, iron II-IV, cobalt II-III, nickel II-III and copper II-III, especially iron II-IV are also of interest.
  • radical X there come into consideration, for example, CH 3 CN, H 2 O, F - , Cl - , Br - , HOO - , O 2 2- , O 2- , R 17 COO - , R 17 O - , LMeO - and LMeOO - , wherein R 17 is hydrogen or unsubstituted or substituted C 1 -C 18 alkyl or aryl, and C 1 -C 18 alkyl, aryl, L and Me have the definitions and preferred meanings given hereinabove and hereinbelow. R 17 is especially hydrogen, C 1 -C 4 alkyl or phenyl, more especially hydrogen.
  • R 17 as C 1 -C 18 alkyl or aryl has the definitions and preferred meanings given hereinabove and hereinbelow.
  • R 17 is especially hydrogen, C 1 -C 4 alkyl or phenyl, more especially hydrogen.
  • the charge of the counter-ion Y is accordingly preferably 1- or 2-, especially 1-.
  • n is preferably an integer having a value of from 1 to 4, preferably 1 or 2 and especially 1.
  • m is preferably an integer having a value of 1 or 2, especially 1.
  • p is preferably an integer having a value of from 0 to 4, especially 2.
  • z is preferably an integer having a value of from 8- to 8+, especially from 4- to 4+ and more especially from 0 to 4+. z is more especially the number 0.
  • q is preferably an integer from 0 to 8, especially from 0 to 4 and is more especially the number 0.
  • R 12 is preferably hydrogen, a cation, C 1 -C 12 alkyl, or phenyl unsubstituted or substituted as indicated above.
  • R 12 is especially hydrogen, an alkali metal cation, alkaline earth metal cation or ammonium cation, C 1 -C 4 alkyl or phenyl, more especially hydrogen or an alkali metal cation, alkaline earth metal cation or ammonium cation.
  • R 13 , R' 13 and R" 13 are preferably hydrogen, C 1 -C 12 alkyl, or phenyl unsubstituted or substituted as indicated above.
  • R 13 , R' 13 and R" 13 are especially hydrogen, C 1 -C 4 alkyl or phenyl, more especially hydrogen or C 1 -C 4 alkyl, preferably hydrogen.
  • Examples of the radical of the formula -N(R 13 )-NR' 13 R" 13 that may be mentioned include -N(CH 3 )-NH 2 and especially -NH-NH 2 .
  • Examples of the radical of the formula -OR 13 that may be mentioned include hydroxyl and C 1 -C 4 alkoxy, such as methoxy and especially ethoxy.
  • R 14 and R 15 together with the nitrogen atom bonding them form a 5- 6- or 7- membered ring it is preferably an unsubstituted or C 1 -C 4 alkyl-substituted pyrrolidine, piperidine, piperazine, morpholine or azepane ring.
  • the piperazine ring can be substituted by C 1 -C 4 alkyl e.g. at the nitrogen atom not bonded to the phenyl radical.
  • R 14 , R 15 and R 16 are preferably hydrogen, unsubstituted or hydroxyl-substituted C 1 -C 12 alkyl, or phenyl unsubstituted or substituted as indicated above.
  • radical of formula -NR 14 R 15 that may be mentioned include -NH 2 , -NHCH 2 CH 2 OH, -N(CH 2 CH 2 OH) 2 , -N(CH 3 )CH 2 CH 2 OH, and the pyrrolidine, piperidine, piperazine, morpholine or azepane ring and also 4-methyl-piperazin-1-yl.
  • R 6 is preferably C 1 -C 12 alkyl; phenyl unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, cyano, nitro, carboxyl, sulfo, hydroxyl, amino, N-mono- or N,N-di-C,-C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, N-phenylamino, N-naphthylamino, phenyl, phenoxy or by naphthoxy; cyano; halogen; nitro; -COOR 12 or -SO 3 R 12 wherein R 12 is in each case hydrogen, a cation, C 1 -C 12 alkyl, or phenyl unsubstituted or substituted as indicated above; -SR 13 , -SO 2 R 13 or -OR 13 wherein R 13 is in each case hydrogen, C 1 -C 12
  • R 6 is especially phenyl unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, phenyl or by hydroxyl; cyano; nitro; -COOR 12 or -SO 3 R 12 wherein R 12 is in each case hydrogen, a cation, C 1 -C 4 alkyl or phenyl; -SR 13 , -SO 2 R 13 or -OR 13 wherein R 13 is in each case hydrogen, C 1 -C 4 alkyl or phenyl; -N(CH 3 )-NH 2 or -NH-NH 2 ; amino; N-mono- or N,N-di-C 1 -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; or an unsubstituted or C 1 -C 4 alkyl-substituted pyrrolidine, piperidine, piperazine, morpholine or a
  • R 6 is very especially C 1 -C 4 alkoxy; hydroxy; phenyl unsubstituted or substituted by C 1- C 4 alkyl, C 1 -C 4 alkoxy, phenyl or by hydroxy; hydrazino; amino; N-mono- or N,N-di-C 1- C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; or an unsubstituted or C 1 -C 4 alkyl-substituted pyrrolidine, piperidine, piperazine, morpholine or azepane ring.
  • radicals R 6 are C 1 -C 4 alkoxy; hydroxy; hydrazino; amino; N-mono- or N,N-di-C 1 -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; or the unsubstituted or C 1 -C 4 alkyl-substituted pyrrolidine, piperidine, piperazine, morpholine or azepane ring.
  • R 6 are C 1 -C 4 alkoxy; hydroxy; N-mono- or N,N-di-C 1 -C 4 alkylamino substituted by hydroxy in the alkyl moiety; or the unsubstituted or C 1 -C 4 alkyl-substituted pyrrolidine, piperidine, piperazine, morpholine or azepane ring, hydroxyl being of particular interest.
  • R 6 The preferred meanings indicated above for R 6 apply also to R 1 , R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9 , R 10 and R 11 , but those radicals may additionally denote hydrogen.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9 , R 10 and R 11 are hydrogen and R 6 is a radical other than hydrogen having the definitions and preferred meanings indicated above.
  • R 1 , R 2 , R 4 , R 5 , R 7 , R 8 , A 10 and R 11 are hydrogen and R 3 , R 6 and R 9 are radicals other than hydrogen having the definitions and preferred meanings indicated above for R 6 .
  • Preferred ligands L are those of formula wherein R' 3 and R' 9 have the definitions and preferred meanings indicated above for R 3 and R 9 , and R' 6 has the definitions and preferred meanings indicated above for R 6 .
  • R' 3 , R' 6 and R' 9 are preferably each independently of the others C 1 -C 4 alkoxy; hydroxy; phenyl unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, phenyl or by hydroxy; hydrazino; amino; N-mono- or N,N-di-C 1 -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety; or an unsubstituted or C 1 -C 4 alkyl-substituted pyrrolidine, piperidine, piperazine, morpholine or azepane ring.
  • the metal complex compounds of formula (1) are known or can be obtained analogously to known processes. They are obtained in a manner known per se by reacting at least one ligand of formula (2) in the desired molar ratio with a metal compound, especially a metal salt, such as the chloride, to form the corresponding metal complex.
  • a metal compound especially a metal salt, such as the chloride
  • the reaction is carried out, for example, in a solvent, such as water or a lower alcohol, such as ethanol, at a temperature of e.g. from 10 to 60°C, especially at room temperature.
  • Ligands of formula (2) that are substituted by hydroxyl can also be formulated as compounds having a pyridone structure in accordance with the following scheme (illustrated here using the example of a terpyridine substituted by hydroxyl in the 4'-position):
  • hydroxyl-substituted terpyridines are also to be understood as including those having a corresponding pyridone structure.
  • the ligands of formula (2) are known or can be prepared in a manner known perse.
  • two parts of pyridine-2-carboxylic acid ester and one part of acetone can be reacted with sodium hydride and the intermediate, a 1,3,5-triketone, obtained after aqueous working-up can be reacted with ammonium acetate to synthesise the central pyridine ring.
  • the corresponding pyridone derivatives are obtained, which can be converted into the chlorine compounds by reaction with a chlorinating agent, such as PCl 5 /POCl 3 .
  • the ligand L of the metal complex compounds of formula (1 a) is especially a compound of formula wherein R' 6 is C 1 -C 12 alkyl; cyano; halogen; nitro; -COOR 12 or -SO 3 R 12 wherein R 12 is in each case hydrogen, a cation, C 1 -C 12 alkyl, or phenyl unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, cyano, nitro, carboxyl, sulfo, hydroxyl, amino, N-mono- or N,N-di-C 1 -C 4 alkylamino unsubstituted or substituted by hydroxy in the alkyl moiety, N-phenylamino, N-naphthylamino, phenyl, phenoxy or by naphthoxy; -SR 13 , -SO 2 R 13 or -OR 13 wherein R 13 is in each case
  • the present invention relates also to the novel ligands of formula
  • the metal complex compounds of formula (1) are preferably used together with peroxy compounds. Examples that may be mentioned in that regard include the following uses:
  • a further use relates to the use of the metal complex compounds of formula (1) as catalysts for reactions with peroxy compounds for bleaching in the context of paper-making. This relates especially to the bleaching of pulp, which can be carried out in accordance with customary processes. Also of interest is the use of the metal complex compounds of formula (1) as catalysts for reactions with peroxy compounds for the bleaching of waste printed paper.
  • aqueous formulations of the metal complex compounds of formula (1) it is preferable to use aqueous formulations of the metal complex compounds of formula (1).
  • metal complex compounds do not cause any appreciable damage to fibres and dyeings, for example in the bleaching of textile material.
  • Processes for preventing the redeposition of migrating dyes in a washing liquor are usually carried out by adding to the washing liquor, which contains a peroxide-containing washing agent, one or more metal complex compounds of formula (1) in an amount of from 0.1 to 200 mg, preferably from 1 to 75 mg, especially from 3 to 50 mg, per litre of washing liquor.
  • the metal complex compounds of formula (1) can alternatively be formed in situ, the metal salt (e.g. manganese(II) salt, such as manganese(II) chloride) and the ligand being added in the desired molar ratios.
  • the present invention relates also to a washing, cleaning, disinfecting or bleaching agent, containing
  • the above percentages are in each case percentages by weight, based on the total weight of the agent.
  • the agents preferably contain from 0.005 to 2 % of a metal complex compound of formula (1), especially from 0.01 to 1 % and preferably from 0.05 to 1 %.
  • the amount thereof is preferably 1 - 50 %, especially 1 - 30 %.
  • the amount thereof is preferably 1 - 70 %, especially 1 - 50 %. Special preference is given to an amount of from 5 to 50 % and especially an amount of from 10 to 50 %.
  • Corresponding washing, cleaning, disinfecting or bleaching processes are usually carried out by using an aqueous liquor comprising a peroxide and from 0.1 to 200 mg of one or more compounds of formula (1) per litre of liquor.
  • the liquor preferably contains from 1 to 30 mg of the compound of formula (1) per litre of liquor.
  • the agents according to the invention can be, for example, a peroxide-containing complete washing agent or a separate bleaching additive.
  • a bleaching additive is used for removing coloured stains on textiles in a separate liquor before the clothes are washed with a bleach-free washing agent.
  • a bleaching additive can also be used in a liquor together with a bleach-free washing agent.
  • the washing or cleaning agent according to the invention can be in solid or liquid form, for example in the form of a liquid, non-aqueous washing agent, comprising not more than 5 % by weight water, preferably comprising from 0 to 1 % by weight water, and, as base, a suspension of a builder substance in a non-ionic surfactant, e.g. as described in GB-A-2 158 454.
  • the washing or cleaning agent is preferably in the form of a powder or, especially, granules.
  • the latter can be prepared, for example, by first preparing an initial powder by spray-drying an aqueous suspension containing all the components listed above except for components D) and E), and then adding the dry components D) and E) and mixing everything together. It is also possible to add component E) to an aqueous suspension containing components A), B) and C), then to carry out spray-drying and then to mix component D) with the dry mass.
  • aqueous suspension that contains components A) and C), but none or only some of component B).
  • the suspension is spray-dried, then component E) is mixed with component B) and added, and then component D) is mixed in in the dry state.
  • the anionic surfactant A) can be, for example, a sulfate, sulfonate or carboxylate surfactant or a mixture thereof.
  • Preferred sulfates are those having from 12 to 22 carbon atoms in the alkyl radical, optionally in combination with alkyl ethoxysulfates in which the alkyl radical has from 10 to 20 carbon atoms.
  • Preferred sulfonates are e.g. alkylbenzenesulfonates having from 9 to 15 carbon atoms in the alkyl radical.
  • the cation in the case of anionic surfactants is preferably an alkali metal cation, especially sodium.
  • Preferred carboxylates are alkali metal sarcosinates of formula R-CO-N(R' 1 )-CH 2 COOM' 1 wherein R is alkyl or alkenyl having from 8 to 18 carbon atoms in the alkyl or alkenyl radical, R' 1 is C 1 -C 4 alkyl and M' 1 is an alkali metal.
  • the non-ionic surfactant B) can be, for example, a condensation product of from 3 to 8 mol of ethylene oxide with 1 mol of a primary alcohol having from 9 to 15 carbon atoms.
  • alkali metal phosphates especially tripolyphosphates, carbonates or hydrogen carbonates, especially their sodium salts, silicates, aluminosilicates, polycarboxylates, polycarboxylic acids, organic phosphonates, aminoalkylenepoly(alkylenephosphonates) or mixtures of those compounds.
  • Especially suitable silicates are sodium salts of crystalline layered silicates of the formula NaHSi t O 2t+1 .pH 2 O or Na 2 Si t O 2t+1 .pH 2 O wherein t is a number from 1.9 to 4 and p is a number from 0 to 20.
  • zeolite A preference is given to those commercially available under the names zeolite A, B, X and HS, and also to mixtures comprising two or more of those components.
  • polycarboxylates preference is given to polyhydroxycarboxylates, especially citrates, and acrylates and also copolymers thereof with maleic anhydride.
  • Preferred polycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid and ethylenediamine disuccinate either in racemic form or in the enantiomerically pure (S,S) form.
  • Phosphonates or aminoalkylenepoly(alkylenephosphonates) that are especially suitable are alkali metal salts of 1-hydroxyethane-1,1-diphosphonic acid, nitrilotris(methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid.
  • peroxide component D there come into consideration, for example, the organic and inorganic peroxides known in the literature and available commercially that bleach textile materials at conventional washing temperatures, for example at from 10 to 95°C.
  • the organic peroxides are, for example, mono- or poly-peroxides, especially organic peracids or salts thereof, such as phthalimidoperoxycaproic acid, peroxybenzoic acid, diperoxydodecanedioic acid, diperoxynonanedioic acid, diperoxydecanedioic acid, diperoxyphthalic acid or salts thereof.
  • organic peracids or salts thereof such as phthalimidoperoxycaproic acid, peroxybenzoic acid, diperoxydodecanedioic acid, diperoxynonanedioic acid, diperoxydecanedioic acid, diperoxyphthalic acid or salts thereof.
  • inorganic peroxides are used, for example persulfates, perborates, percarbonates and/or persilicates. It will be understood that mixtures of inorganic and/or organic peroxides can also be used.
  • the peroxides may be in a variety of crystalline forms and have different water contents, and they may also be used together with other inorganic or organic compounds in order to improve their storage stability.
  • the peroxides are added to the agent preferably by mixing the components, for example using a screw metering system and/or a fluidised bed mixer.
  • the agents may comprise, in addition to the combination according to the invention, one or more optical brighteners, for example from the class bis-triazinylamino-stilbenedisulfonic acid, bis-triazolyl-stilbenedisulfonic acid, bis-styryl-biphenyl or bis-benzofuranylbiphenyl, a bis-benzoxalyl derivative, bis-benzimidazolyl derivative or coumarin derivative or a pyrazoline derivative.
  • optical brighteners for example from the class bis-triazinylamino-stilbenedisulfonic acid, bis-triazolyl-stilbenedisulfonic acid, bis-styryl-biphenyl or bis-benzofuranylbiphenyl, a bis-benzoxalyl derivative, bis-benzimidazolyl derivative or coumarin derivative or a pyrazoline derivative.
  • the agent may also comprise suspending agents for dirt, e.g. sodium carboxymethylcellulose, pH regulators, e.g. alkali metal or alkaline earth metal silicates, foam regulators, e.g. soap, salts for regulating the spray-drying and the granulating properties, e.g. sodium sulfate, perfumes and, optionally, antistatic agents and softeners, enzymes, such as amylase, bleaches, pigments and/or toning agents. Such constituents must especially be stable towards the bleaching agent used.
  • bleach-activating active ingredients and/or conventional bleach activators, that is to say compounds that, under perhydrolysis conditions, yield unsubstituted or substituted perbenzo- and/or peroxo-carboxylic acids having from 1 to 10 carbon atoms, especially from 2 to 4 carbon atoms.
  • Suitable bleach activators include the customary bleach activators, mentioned at the beginning, that carry O- and/or N-acyl groups having the indicated number of carbon atoms and/or unsubstituted or substituted benzoyl groups.
  • polyacylated alkylenediamines espe-' cially tetraacetylethylenediamine (TAED), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N,N-diacetyl-N,N-dimethylurea (DDU), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), compounds of formula (4): wherein R' 1 is a sulfonate group, a carboxylic acid group or a carboxylate group, and wherein R' 2 is linear or branched (C 7 -C 15 )alkyl, especially activators known under the names SNOBS, SLOBS and DOBA, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-
  • polymers which, during the washing of textiles, prevent staining caused by dyes in the washing liquor that have been released from the textiles under the washing conditions.
  • Such polymers are preferably polyvinylpyrrolidones or polyvinylpyridine-N-oxides whch may have been modified by the incorporation of anionic or cationic substituents, especially those having a molecular weight in the range of from 5000 to 60 000, more especially from 10 000 to 50 000.
  • Such polymers are preferably used in an amount of from 0.05 to 5 % by weight, especially:from 0.2 to 1.7 % by weight, based on the total weight of the washing agent.
  • the invention relates also to granules that comprise the catalysts according to the invention and are suitable for incorporation into a powder- or granule-form washing, dishwashing, cleaning or bleaching agent.
  • Such granules preferably comprise:
  • binder (b) there come into consideration anionic dispersants, non-ionic dispersants, polymers and waxes that are water-soluble, dispersible or emulsifiable in water.
  • the anionic dispersants used are, for example, commercially available water-soluble anionic dispersants for dyes, pigments etc..
  • the following products come into consideration: condensation products of aromatic sulfonic acids and formaldehyde, condensation products of aromatic sulfonic acids with unsubstituted or chlorinated diphenylene or diphenyl oxides and optionally formaldehyde, (mono-/di-)alkylnaphthalenesulfonates, sodium salts of polymerised organic sulfonic acids, sodium salts of polymerised alkylnaphthalenesulfonic acids, sodium salts of polymerised alkylbenzenesulfonic acids, alkylarylsulfonates, sodium salts of alkyl polyglycol ether sulfates, polyalkylated polynuclear arylsulfonates, methylene-linked condensation products of arylsulfonic acids and hydroxyarylsulfonic acids, sodium salt
  • Especially suitable anionic dispersants are condensation products of naphthalenesulfonic acids with formaldehyde, sodium salts of polymerised organic sulfonic acids, (mono-/di-)-alkylnaphthalenesulfonates, polyalkylated polynuclear arylsulfonates, sodium salts of polymerised alkylbenzenesulfonic acids, lignosulfonates, oxytignosuifonates and condensation' products of naphthatenesutfonic acid with a polychloromethyldiphenyl.
  • Suitable non-ionic dispersants are especially compounds having a melting point of, preferably, at least 35°C that are emulsifiable, dispersible or soluble in water, for example the following compounds:
  • Especially suitable non-ionic dispersants are surfactants of formula R' 11 -O-(alkylene-O) n -R' 12 (5), wherein R' 11 is C 8 -C 22 alkyl or C 8 -C 18 alkenyl; R' 12 is hydrogen; C 1 -C 4 alkyl; a cycloaliphatic radical having at least 6 carbon atoms; or benzyl; "alkylene” is an alkylene radical having from 2 to 4 carbon atoms and n is a number from 1 to 60.
  • a substituent R' 11 or R' 12 in formula (5) is advantageously the hydrocarbon radical of an unsaturated or, preferably, saturated aliphatic monoalcohol having from 8 to 22 carbon atoms.
  • the hydrocarbon radical may be straight-chain or branched.
  • R' 11 and R' 12 are preferably each independently of the other an alkyl radical having from 9 to 14 carbon atoms.
  • Aliphatic saturated monoalcohols that come into consideration include natural alcohols, e.g. lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, and also synthetic alcohols, e.g. 2-ethylhexanol, 1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol, trimethylhexanol, trimethylnonyl alcohol, decanol, C 9 -C 11 oxo-alcohol, tridecyl alcohol, isotridecyl alcohol and linear primary alcohols (Alfols) having from 8 to 22 carbon atoms. Some examples of such Alfols are Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) and Alfol (16-18). (“Alfol" is a registered trade mark).
  • Unsaturated aliphatic monoalcohols are, for example, dodecenyl alcohol, hexadecenyl alcohol and oleyl alcohol.
  • the alcohol radicals may be present singly or in the form of mixtures of two or more components, e.g. mixtures of alkyl and/or alkenyl groups that are derived from soybean fatty acids, palm kernel fatty acids or tallow oils.
  • Alkylene-O chains are preferably divalent radicals of the formulae -(CH 2 -CH 2 -O)-,
  • cycloaliphatic radical examples include cycloheptyl, cyclooctyl and preferably cyclohexyl.
  • non-ionic dispersants correspond to formula wherein R 15 is C 9 -C 14 alkyl; R 16 is C 1 -C 4 alkyl; Y 5 , Y 6 , Y 7 and Y 8 are each independently of the others hydrogen, methyl or ethyl, one of the radicals Y 5 , Y 6 and one of the radicals Y 7 , Y 8 always being hydrogen; and n 4 and n 5 are each independently of the other an integer from 4 to 8.
  • non-ionic dispersants of formulae (5) to (7) can be used in the form of mixtures.
  • surfactant mixtures there come into consideration non-end-group-terminated fatty alcohol ethoxylates of formula (5), e.g. compounds of formula (5) wherein
  • non-ionic dispersants of formulae (5), (6) and (7) include reaction products of a C 10 -C 13 fatty alcohol, e.g. a C 13 oxo-alcohol, with from 3 to 10 mol of ethylene oxide, propylene oxide and/or butylene oxide or the reaction product of one mol of a C 13 fatty alcohol with 6 mol of ethylene oxide and 1 mol of butylene oxide, it being possible for the addition products each to be end-group-terminated with C 1 -C 4 alkyl, preferably methyl or butyl.
  • Such dispersants can be used singly or in the form of mixtures of two or more dispersants.
  • the granules according to the invention may comprise a water-soluble organic polymer as binder.
  • a water-soluble organic polymer as binder.
  • Such polymers may be used singly or in the form of mixtures of two or more polymers.
  • Water-soluble polymers that come into consideration are, for example, polyethylene glycols, copolymers of ethylene oxide with propylene oxide, gelatin, polyacrylates, polymethacrylates, polyvinylpyrrolidones, vinylpyrrolidones, vinyl acetates, polyvinylimidazoles, polyvinylpyridine-N-oxides, copolymers of vinylpyrrolidone with long-chain ⁇ -olefins, copolymers of vinylpyrrolidone with vinylimidazole, poly(vinylpyrrolidone/dimethylaminoethyl methacrylates), copolymers of vinylpyrrolidone/dimethylaminopropyl methacrylamides, copolymers of vinylpyrrolidone/dimethylaminopropyl acrylamides, quatemised copolymers of vinylpyrrolidones and dimethylaminoethyl methacrylates, terpolymers of vinylcap
  • polyethylene glycols carboxymethylcellulose
  • polyacrylamides polyvinyl alcohols
  • polyvinylpyrrolidones gelatin
  • hydrolysed polyvinyl acetates copolymers of vinylpyrrolidone and vinyl acetate
  • polyacrylates copolymers of ethyl acrylate with methacrylate and methacrylic acid, and polymethacrylates.
  • Suitable water-emulsifiable or water-dispersible binders also include paraffin waxes.
  • Encapsulating materials (c) include especially water-soluble and water-dispersible polymers and waxes. Of those materials, preference is given to polyethylene glycols, polyamides, polyacrylamides, polyvinyl alcohols, polyvinylpyrrolidones, gelatin, hydrolysed polyvinyl acetates, copolymers of vinylpyrrolidone and vinyl acetate, and also polyacrylates, paraffins, fatty acids, copolymers of ethyl acrylate with methacrylate and methacrylic acid, and polymethacrylates.
  • additives (d) that come into consideration are, for example, wetting agents, dust removers, water-insoluble or water-soluble dyes or pigments, and also dissolution accelerators, optical brighteners and sequestering agents.
  • the anionic or non-ionic dispersant and/or the polymer and, if appropriate, the further additives are dissolved in water and stirred, if desired with heating, until a homogeneous solution has been obtained.
  • the catalyst according to the invention is then dissolved or suspended in the resulting aqueous solution.
  • the solids content of the solution should preferably be at least 30 % by weight, especially 40 to 50 % by weight, based on the total weight of the solution.
  • the viscosity of the solution is preferably less than 200 mPas.
  • the aqueous solution so prepared, comprising the catalyst according to the invention is then subjected to a drying step in which all water, with the exception of a residual amount, is removed, solid particles (granules) being formed at the same time.
  • a drying step in which all water, with the exception of a residual amount, is removed, solid particles (granules) being formed at the same time.
  • Known methods are suitable for producing the granules from the aqueous solution. In principle, both continuous methods and discontinuous methods are suitable. Continuous methods are preferred, especially spray-drying and fluidised bed granulation processes.
  • spray-drying processes in which the active ingredient solution is sprayed into a chamber with circulating hot air.
  • the atomisation of the solution is effected e.g. using unitary or binary nozzles or is brought about by the spinning effect of a rapidly rotating disc.
  • the spray-drying process may be combined with an additional agglomeration of the liquid particles with solid nuclei in a fluidised bed that forms an integral part of the chamber (so-called fluid spray).
  • the fine particles ( ⁇ 100 ⁇ m) obtained by a conventional spray-drying process may, if necessary after being separated from the exhaust gas flow, be fed as nuclei, without further treatment, directly into the atomizing cone of the atomiser of the spray-dryer for the purpose of agglomeration with the liquid droplets of the active ingredient.
  • the water can rapidly be removed from the solutions comprising the catalyst according to the invention, binder and further additives. It is expressly intended that agglomeration of the droplets forming in the atomising cone, or the agglomeration of droplets with solid particles, will take place.
  • the granules formed in the spray-dryer are removed in a continuous process, for example by a sieving operation.
  • the fines and the oversize particles are either recycled directly to the process (without being redissolved) or are dissolved in the liquid active ingredient formulation and subsequently granulated again.
  • a further preparation method is a process in which the polymer is mixed with water and then the catalyst is dissolved/suspended in the polymer solution, thus forming an aqueous phase, the catalyst according to the invention being homogeneously distributed in that phase.
  • the aqueous phase is dispersed in a water-immiscible liquid in the presence of a dispersion stabiliser in order that a stable dispersion is formed.
  • the water is then removed from the dispersion by distillation, forming substantially dry particles. In those particles, the catalyst is homogeneously distributed in the polymer matrix.
  • the granules according to the invention are wear-resistant, low in dust, pourable and readily meterable. They can be added directly to a formulation, such as a washing agent formulation, in the desired concentration of the catalyst according to the invention.
  • the coloured appearance of the granules in the washing agent is to be suppressed, this can be achieved, for example, by embedding the granules in a droplet of a whitish meltable substance ("water-soluble wax") or by adding a white pigment (e.g. TiO 2 ) to the granule formulation or, preferably, by encapsulating the granules in a melt consisting, for example, of a water-soluble wax, as described in EP-A-0 323 407, a white solid being added to the melt in order to reinforce the masking effect of the capsule.
  • a white pigment e.g. TiO 2
  • the catalyst according to the invention is dried in a separate step prior to the melt-granulation and, if necessary, dry-ground in a mill so that all the solids particles are ⁇ 50 ⁇ m in size.
  • the drying is carried out in an apparatus customary for the purpose, for example in a paddle dryer, vacuum cabinet or freeze-dryer.
  • the finely particulate catalyst is suspended in the molten carrier material and homogenised.
  • the desired granules are produced from the suspension in a shaping step with simultaneous solidification of the melt.
  • the choice of a suitable melt-granulation process is made in accordance with the desired size of granules. In principle, any process which can be used to produce granules in a particle size of from 0.1 to 4 mm is suitable. Such processes are droplet processes (with solidification on a cooling belt or during free fall in cold air), melt-prilling (cooling medium gas/liquid), and flake formation with a subsequent comminution step, the granulation apparatus being operated continuously or discontinuously.
  • the coloured appearance of the granules prepared from a melt is to be suppressed in the washing agent, in addition to the catalyst it is also possible to suspend in the melt white or coloured pigments which, after solidification, impart the desired coloured appearance to the granules (e.g. titanium dioxide).
  • the melt white or coloured pigments which, after solidification, impart the desired coloured appearance to the granules (e.g. titanium dioxide).
  • the granules can be covered or encapsulated in an encapsulating material.
  • Methods suitable for such an encapsulation include the customary methods and also the encapsulation of the granules by a melt consisting e.g. of a water-soluble wax, as described, for example, in EP-A-0 323 407, coacervation, complex coacervation and surface polymerisation.
  • Encapsulating materials (c) include e.g. water-soluble, water-dispersible or water-emulsifiable polymers and waxes.
  • Further additives (d) include e.g. wetting agents, dust-removers, water-insoluble or water-soluble dyes or pigments, and also dissolution accelerators, optical brighteners and sequestering agents.
  • the metal complex compounds of formula (1) also exhibit a markedly improved bleach-catalysing action on coloured stains on hard surfaces.
  • a dishwashing agent that comprises a peroxy compound and optionally TAED (N,N,N',N'-tetraacetylethylenediamine) results in the substantial removal of e.g. tea stains on china. This is the case even when hard water is used, it being known that tea deposits are more difficult to remove in hard water than in soft water.
  • the compounds are also very suitable for cleaning hard surfaces at low temperatures.
  • metal complex compounds of formula (1) as catalysts for reactions with peroxy compounds in cleaning solutions for hard surfaces, especially for kitchen- and table-ware, is therefore of special interest.
  • the present invention relates also to cleaning agents for hard surfaces, especially cleaning agents for table- and kitchen-ware and, among such agents, preferably those for use in cleaning processes carried out by machine, which agents comprise one of the above-described metal complex compounds of formula (1) as bleach catalyst.
  • Suitable formulations for such cleaning agents include, for example, the formulations mentioned above for the washing agents.
  • the metal complex compounds of formula (1) also have, together with peroxy compounds, excellent antibacterial action.
  • the use of the metal complex compounds of formula (1) for killing bacteria or for protecting against bacterial attack is therefore likewise of interest.
  • the metal complex compounds of formula (1) are also outstandingly suitable for selective oxidation in the context of organic synthesis, especially the oxidation of organic molecules, e.g. of olefins to form epoxides. Such selective transformation reactions are required especially in process chemistry.
  • the invention accordingly relates also to the use of the metal complex compounds of formula (1) in selective oxidation reactions in the context of organic synthesis.
  • Example 1 1'H-[2,2';6',2"]Terpyridin-4'-one (referred to as L1 below)
  • a solution in 20 ml of dichloromethane of 1.61 g (6 mmol) of 4'-chloro-2,2':6',2"-terpyridine and 20 ml of N-methylaminoethanol are added in succession to a solution of 1.35 g (6.8 mmol) of iron(II) chloride tetrahydrate in 100 ml of isopropanol.
  • the mixture is then boiled at reflux for 20 hours.
  • the mixture is concentrated and a solution of 1.66 g of ammonium hexafluorophosphate in 10 ml of methanol is added.
  • the resulting violet precipitate is washed four times using 50 ml of diethyl ether each time and once with 50 ml of water.
  • Example 8 4'-(4-Methyl-piperazin-1-yl)-[2,2';6',2"]terpyridine (referred to as L8 below)
  • Example 8b 1,1-Dimethyl-4-[2,2;6',2"]terpyridin-4'-yl-piperazin-1-ium iodide (referred to as L8b below)
  • ligand L8 211 mg (0.64 mmol) of ligand L8 are dissolved in 11 ml of acetonitrile and at room temperature an excess of methyl iodide (2.1 ml) is added dropwise thereto. The mixture is then stirred for 3 hours at room temperature and concentrated, and 10 ml of dichloromethane are added to the residue. The precipitate is filtered off and dried in vacuo, 1,1-dimethyl-4-[2,2';6',2"]terpyridin-4'-yl-piperazin-1-ium iodide, beige solid.
  • Example 10 4'-Piperidin-1-yl-[2,2';6',2"]terpyridine (referred to as L10 below)
  • Example 13 4'-(4-Isopropyl-phenyl)-[2,2';6',2"]terpyridine (referred to as L13 below)
  • This compound is prepared analogously to the procedure described above for the preparation of the ligand L12 in Example 12, but 4-isopropyl benzaldehyde is used as carbonyl component. 4'-(4-Isopropyl-phenyl)-[2,2';6',2"]terpyridine, white solid.
  • Example 14 4'-p-Tolyl-[2,2';6',2"]terpyridine (referred to as L14 below)
  • This compound is prepared analogously to the procedure described above for the preparation of the ligand L12 in Example 12, but 4-phenyl benzaldehyde is used as carbonyl component. 4'-Biphenyl-4-yl-[2,2 ;6',2"]terpyridine, white solid.
  • This compound is obtained in a manner analogous to that described in Example 16, except that in Step 2 ethanol is used instead of methanol and the mixture is heated at reflux for 24 hours after the addition of alcohol.
  • the purification of the crude product is effected by distillation (100-105°C, 0.08 mbar).
  • 4-Ethoxy-pyridine-2-carboxylic acid ethyl ester is obtained in the form of a colourless oil.
  • This compound is prepared in a manner analogous to that described in Example 1, Step 1, for pyridine-2-carboxylic acid ethyl ester, but instead 4-chloro-pyridine-2-carboxylic acid methyl ester from Example 16 is used.
  • the beige solid crude product is used for further syntheses without special purification steps.
  • This compound is prepared in a manner analogous to that described in Example 1, Step 1, for pyridine-2-carboxylic acid ethyl ester, but instead 4-ethoxy-pyridine-2-carboxylic acid ethyl ester from Example 17 is used.
  • the yellowish crude product is used for further syntheses without special purification steps.
  • This compound is prepared in a manner analogous to that described in Example 1, Step 1, for pyridine-2-carboxylic acid ethyl ester, but instead 4-pyrrolidin-1-yl-pyridine-2-carboxylic acid ethyl ester from Example 18 is used.
  • the yellow-orange crude product is used for further syntheses without special purification steps.
  • This compound is prepared in a manner analogous to that described in Example 1, Step 2 for 1,5-di-pyridin-2-yl-pentane-1,3,5-trione, but instead the ethoxy-substituted triketone from Example 20 is used.
  • Pure 4,4"-diethoxy-1'H-[2,2';6',2"]terpyridin-4'-one can be obtained by chromatography on silica gel (chloroform/methanol 9:1, 0.1 % NH 4 OH) in the form of a white crystalline powder.
  • This compound is prepared in a manner analogous to that described in Example 1, Step 2 for 1,5-di-pyridin-2-yl-pentane-1,3,5-trione, but instead the pyrrolidine-substituted triketone from Example 21 is used. Pure 4,4"-di-pyrrolidin-1-yl-1'H-[2,2';6',2"]terpyridin-4'-one can be obtained by recrystallisation from methanol in the form of an almost colourless solid.
  • This compound is prepared in a manner analogous to that described in Example 6 for 4'-pyrrolidin-1-yl-[2,2';6',2"]terpyridine, but instead 2-(N-methylamino)ethanol is used as amine and 4,4"-dichloro-1'H-[2,2';6',2"]terpyridin-4'-one from Example 22 is used as precursor.
  • 1 H-NMR 360 MHz, DMSO-d6): 3.12 (s, 6H); 3.20-4.00 (m, 8H); 6.73-6.82 (m, 2H); 7.70-7.95 (m, 4H); 8.23 (d, 2H, 5.9 Hz).
  • Example 27 4'-Methoxy-4,4"-di-pyrrolidin-1-yl-[2,2';6',2"]terpyridine (referred to as L21 below)
  • This compound is prepared in a manner analogous to that described in Example 7 with 4'-chloro-[2,2';6',2"]terpyridine, but instead the trichloro-substituted terpyridine L22 from Example 28, and pyrrolidine as amine component are used. 4,4',4"-Tri-pyrrolidin-1-yl-[2,2';6',2"]terpyridine, beige powder.
  • This compound is prepared in a manner analogous to that described in Example 7 with 4'-chloro-[2',2';6',2"]terpyridine, but instead the trichloro-substituted terpyridine L22 from Example 28, and 2-methylaminoethanol as amine component are used.
  • This compound is prepared in a manner analogous to that described in Example 7 with 4'-chloro-[2,2';6',2"]terpyridine, but instead the chloro-substituted terpyridine L26 from Example 32, arid pyrrolidine as amine component are used. 4,4"-Diethoxy-4'-pyrrolidin-1-yl-[2,2';6',2"]terpyridine, white solid.
  • This compound is prepared in a manner analogous to that described in Example 7 with 4'-chloro-[2,2';6',2"]terpyridine, but instead the chloro-substituted terpyridine L26 from Example 32 is used as amine component. Recrystallisation from methanol yields 2-[(4,4"-diethoxy-[2,2';6',2"]terpyridin-4'-yl)-(2-hydroxy-ethyl)-amino]-ethanol in the form of a white solid.
  • Example 36 6,6"-Bis(2-hydroxyphenyl)-2,2':6',2"-terpyridine (referred to as L30 below)
  • Example 37 Manganese(II) complex containing a pyridone ligand: ⁇ [2,2';6',2"]terpyridin-4'-ol ⁇ manganese(II) chloride.
  • Example 38 Manganese(II) complex with a substituted terpyridine ligand: (2-[(2-hydroxyethyl)-[2,2';6',2"]terpyridin-4'-yl-amino]-ethanol ⁇ manganese(II) chloride
  • Example 38a ⁇ 2-(Methyl-[2,2';6',2"]terpyridin-4'-yl-amino)-ethanol ⁇ manganese(II) chloride
  • Example 39 Manganese(II) complex with two substituted terpyridine ligands: bis ⁇ 2-[(2-hydroxy-ethyl)-[2,2';6',2"]terpyridin-4'-yl-amino]-ethanol ⁇ manganese(II) chloride
  • Example 40 Bis ⁇ 4,4"-bis[(2-hydroxy-ethyl)-methyl-amino]-[2,2';6',2"]terpyridin-4'-ol ⁇ -manganese(ll) chloride
  • Example 41 1.78 g (7.14 mmol) of 1'H-[2,2';6',2"]terpyridin-4'-one L1 are added to a solution of 1.75 g (7.14 mmol) of manganese(II) acetate tetrahydrate in 35 ml of water. Then a solution of 3.28 g (9.93 mmol of active oxygen as KHSO 5 ) of potassium peroxomonosulfate in 20 ml of water is added dropwise thereto. The mixture is then stirred for 2 hours at room temperature, then filtered with suction and washed with 25 ml of water.
  • Example 42 1.23 g (5 mmol) of manganese(II) acetate tetrahydrate are added to a suspension of 1.68 g (5 mmol) of 2-[(2-hydroxy-ethyl)-[2,2';6',2"]terpyridin-4'-yl-amino]-ethanol L7. A solution of 1.44 g (4.37 mmol of active oxygen as KHSO 5 ) of potassium peroxomonosulfate in 30 ml of water is then added dropwise. To the resulting red solution there is then added dropwise a total of 25 ml of 1 M ammonium hexafluorophosphate solution.
  • Example 43 99 mg (0.5 mmol) of manganese(II) chloride tetrahydrate are added to a suspension of 168 mg (0.5 mmol) of 2-[(2-hydroxy-ethyl)-[2,2';6',2"]terpyridin-4'-yl-amino]-ethanol L7. A solution of 144 mg (0.44 mmol of active oxygen as KHSO 5 ) of potassium peroxomonosulfate in 3 ml of water is then added dropwise. The almost black solid is filtered off and dried at 50°C in vacuo.
  • the solutions are exposed at 40°C to a hydrogen peroxide concentration of 8.6 mM for 30 minutes.
  • the optical density is determined by means of the respective UV/VIS spectrum at the wavelength indicated in Table 1 below and is a measure of the stability.
  • the Mn complex of formula (137) given in Table 1 below is the compound of formula Table 1
  • the above Example shows that the manganese complex with substituted terpyridine has markedly greater stability in comparison with the manganese complex with unsubstituted terpyridine.
  • the complex has largely decomposed after 30 minutes, and the UV/VIS spectrum obtained is virtually the same as that of the ligand (terpyridine), whereas the manganese complex with the substituted terpyridine is stable.
  • 7.5 g of white cotton fabric and 2.5 g of tea-stained cotton fabric are treated in 80 ml of washing liquor.
  • the liquor contains a standard washing agent (ECE, 456 IEC) in a concentration of 7.5 g/l.
  • ECE standard washing agent
  • the hydrogen peroxide concentration is 8.6 mmol/l.
  • the catalyst concentration (1:1 complex of manganese(II) chloride tetrahydrate with the ligand in question, prepared in methanolic solution with the addition of a small amount of lithium hydroxide) is 50 ⁇ mol/l.
  • the washing process is carried out in a steel beaker in a LINITEST : apparatus for 30 minutes at 40°C.
  • the increase in the lightness DY (difference in lightness according to CIE) of the stains brought about by the treatment is determined spectrophotometrically in comparison with values obtained without the addition of catalyst.
  • Table 2 1:1 Mn complex with ligand DY increase
  • Ligand DY increase L1 5.0 L10 4.4 L4 5.0 L11 5.5 L5 5.2 L17 5.3 L6 5.8 L18 3.0 L7 5.6 L19 5.3 1)
  • the manganese complexes exhibit a very good bleaching action.
  • the temperature of the solution is raised from 23° to 53°C over a period of 12 minutes and maintained at the final temperature for 23 minutes. After rinsing and drying in air, the results are evaluated visually on a scale of 1 (no cleaning) to 10 (clean).
  • the catalyst-free system is used as reference.
  • TAED is a commercially available bleach activator which is included in Table 4 for comparison purposes.
  • the liquors comprising the manganese complex can be used for further bleaching cycles without any appreciable reduction in the bleaching action.
  • the redeposition of dyes in washing liquors should be avoided.
  • 7.5 g of white cotton fabric are treated in 80 ml of washing liquor.
  • the liquor contains a standard washing agent (ECE, 456 IEC) in a concentration of 7.5 g/l.
  • the hydrogen peroxide concentration is 8.6 mmol/l.
  • the catalyst concentration (of manganese(II) chloride tetrahydrate with the ligand, prepared in methanolic solution with the addition of a small amount of lithium hydroxide) is 50 ⁇ mol/l, and a solution of the test dye Direct Brown 172 having 10 mg/l of the 250% formulation.
  • the washing process is carried out in a steel beaker in a LINITEST apparatus for 30 minutes at 40°C.
  • the DTI activity is determined.
  • the reflection spectra of the samples were measured using a SPECTRAFLASH 2000 and converted into lightness values (D65/10) in accordance with a standard CIE procedure.
  • Application Example 9 The use of the catalysts according to the invention causes hardly any additional fading of the dyes in dyed cotton laundry. When used as described above in Application Example 8, after treatment five times, on average, virtually no losses of dye are recorded. The values given in the following Table are relative percentage dye losses, determined on the basis of Kubelka-Munk values at the respective absorption maximum. Table 8 Cotton dyeing with dye Dye loss (%) in system with Mn-L7 (50 ⁇ M) without catalyst Cibanone Brown BR 0 0 Cibanone Blue RS 3 2 Procion Brown H-4RD 9 11 Levafix Scarlet E-2GA 10 10
  • the mixture is then left for 14 hours at room temperature, then diluted with diethyl ether and the phases are separated.
  • the organic extract is dried over sodium sulfate, filtered and concentrated.
  • the catalytic turnover number for the epoxide formed, ethyl oxirane-2-carboxylate is determined by comparing the intensity of the epoxide methine proton at 3.34-3.38 ppm with the ligand signal L7 at 8.53 ppm as reference and is 35 ⁇ 8.

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EP1383857A2 (en) 2004-01-28
US20090068282A1 (en) 2009-03-12
CN100567471C (zh) 2009-12-09
ES2265041T3 (es) 2007-02-01
KR100889467B1 (ko) 2009-03-20
DE60211884D1 (de) 2006-07-06
CN1646672A (zh) 2005-07-27
WO2002088289A3 (en) 2003-02-27
US8044013B2 (en) 2011-10-25
US7456285B2 (en) 2008-11-25
BR0209292A (pt) 2004-07-13
US20040142843A1 (en) 2004-07-22
JP2004533918A (ja) 2004-11-11
US20060264633A1 (en) 2006-11-23
WO2002088289A2 (en) 2002-11-07
BR0209292B1 (pt) 2014-04-29
JP4414653B2 (ja) 2010-02-10
KR20040015213A (ko) 2004-02-18
US7161005B2 (en) 2007-01-09
DE60211884T2 (de) 2006-11-23
ATE328057T1 (de) 2006-06-15
US7692004B2 (en) 2010-04-06
MXPA03009905A (es) 2004-01-29
US20080262225A1 (en) 2008-10-23

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